Process for polymerization of olefins

ABSTRACT

A catalyst for olefin polymerization, comprising:
         a solid catalyst component comprising   [A] a solid component having substantially no hydroxyl group,   [B] a compound of a transition metal selected from Groups 3-11 of the Periodic Table, and   [C] a mixture of an activator compound (C-1) capable of reacting with the transition metal compound [B] to form a metal complex having catalytic activity and an organoaluminum compound (C-2); and   [D] an organomagnesium compound soluble in a hydrocarbon solvent which is obtained by reacting (i) an organomagnesium compound represented by the general formula:
 
(Mt) α (Mg) β (R 1 ) a (R 2 ) b 
 
wherein Mt is a metal atom belonging to Groups 1-3 of the Periodic Table, R 1  and R 2  are hydrocarbon groups of 2-20 carbon atoms, and α, β, a and b are numerals satisfying the following relationship: 0≦α, 0&lt;β, 0≦a, 0&lt;b, a+b&gt;0, and rα+2β=a+b (where r is a valence of Mt) with (ii) a compound selected from an amine, an alcohol and a siloxane.

TECHNICAL FIELD

The present invention relates to a catalyst for olefin polymerizationand a method for polymerizing olefins using said catalyst.

BACKGROUND ART

Hitherto, so-called Ziegler-Natta catalysts comprising a titaniumcompound and an organoaluminum compound have been known as catalysts forproducing polymers or copolymers of olefins. On the other hand,recently, a technology has been found wherein homopolymerization ofethylene or copolymerization of ethylene with other α-olefins can beperformed with high activity by using catalysts comprising a so-calledmetallocene compound such as bis(cyclopentadienyl)zirconium dichlorideand an aluminoxane which is a kind of organoaluminumoxy compounds. Thedetails of this technology are disclosed in JP-B-4-12283 (correspondingto DE 3127133.2).

On the other hand, as catalyst systems using activators other than theorganoaluminumoxy compounds, Taube et al. report in J. Organometall.Chem., 347. C9(1988) carrying out polymerization of ethylene using acompound represented by [Cp₂TiMe(THF)]⁺[BPh₄]⁻ (Cp: cyclopentadienylgroup, Me: methyl group, Ph: phenyl group, THF: tetrahydrofuran). Jordanet al. report in J. Am. Chem. Soc., 109. 4111(1987) that ethylene ispolymerized using a zirconium complex represented by [Cp₂ZrR(L)]⁺ (R:methyl group or benzyl group, L: Lewis base).

Furthermore, JP-A-1-501950 and JP-A-1-502036 disclose a method forpolymerizing olefins using a catalyst comprising a cyclopentadienylmetal compound and an ionic compound capable of stabilizing acyclopentadienyl metal cation.

In addition, JP-A-5-301917, JP-A-6-136047, JP-A-9-59310, JP-A-11-269222,etc. disclose catalyst systems using organoaluminum compounds and clays,clay minerals or ion-exchangeable laminar compounds as activators.

In general, when olefins are polymerized by using these metallocenecatalysts, alkylaluminums such as triethylaluminum andtriisobutylaluminum ordinarily used in Ziegler-Natta catalysts are usedtogether with the metallocene catalysts. The alkylaluminums are thematerials that serve to remove impurities in the polymerization systemwhich become catalyst poisons, i.e. scavengers, and are added to thepolymerization system in order to maintain high activity.

As methods for polymerization of olefins using the metallocene catalystand the alkylaluminum, JP-A-3-179005 discloses polymerization of olefinsin the presence of a catalyst comprising a neutral metallocene compound,an alkylaluminum and a Lewis acid, JP-A-3-207704 discloses a method ofpolymerization of olefins which includes mixing a metallocene catalystprepared from a neutral metallocene compound and an ionic compound withan aluminumalkyl-olefin mixture, and JP-A-5-505838 disclosespolymerization of olefins in the presence of a catalyst containing thereaction product of a group IV metal compound of bis(cyclopentadienyl)having a proton reactive substituent with a compound of a cation havinga donatable proton and an activator, and a compound of a Group IIIAelement.

However, as disclosed in Journal of Organometallic Chemistry 497 (1995)55-59, in the presence of an excess amount of trimethylaluminum ortriethylaluminum, the catalysts are poisoned and thus have lowerpolymerization activity. Therefore, there is a problem that thescavengers for displaying the activity in metallocene catalysts can beeffectively used only when their concentration is in a specific narrowrange and thus it is difficult to maintain the polymerization activityat a high level.

As a result of intensive research conducted by the present inventors, ithas been found that when specific organomagnesium compounds are used asthe scavenger, the reduction in the polymerizing activity of thecatalyst does not occur regardless of the scavenger concentration, thusthe high polymerizing activity of the catalyst can be maintained in awide range of the scavenger concentration. Thus, the present inventionhas been accomplished.

The object of the present invention is to provide a catalyst for olefinpolymerization comprising a scavenger which can maintain a highpolymerization activity of the catalyst in a wide range of scavengerconcentration and a method for polymerization of olefins using saidcatalyst, that can provide a polymer powder which does not cause anyphenomena, such as deposition on the reactor during the polymerization,and has excellent particle properties.

DISCLOSURE OF INVENTION

Under the circumstances, the present inventors have conducted intensiveresearch in an attempt to find a catalyst for olefin polymerizationwhich contains a scavenger which can maintain a high polymerizationactivity of the catalyst in a wide range of scavenger concentration andthat provides a polymer powder causing no phenomena such as depositionon the reactor during polymerization and having excellent particleproperties. As a result, they have accomplished the present invention.

That is, the present invention includes the following embodiments.

1) A catalyst for olefin polymerization, comprising:

a solid catalyst component comprising:

[A] a solid component having substantially no hydroxyl group,

[B] a compound of a transition metal selected from metals of Groups 3-11of the Periodic Table, and

[C] a mixture of an activator compound (C-1) capable of reacting withthe transition metal compound [B] to form a metal complex havingcatalytic activity and an organoaluminum compound (C-2); and

[D] an organomagnesium compound soluble in a hydrocarbon solvent whichis obtained by reacting (i) an organomagnesium compound represented bythe general formula:(Mt)_(α)(Mg)_(β)(R¹)_(a)(R²)_(b)wherein Mt is a metal atom belonging to Groups 1-3 of the PeriodicTable, R¹ and R² are hydrocarbon groups of 2-20 carbon atoms, and α, β,a and b are numerals satisfying the following relationship 0≦α, 0<β,0≦a, 0≦b, a+b>0, and rα+2β=a+b (where r is a valence of Mt) with (ii) acompound selected from amine, alcohol and siloxane compounds.

2) A catalyst for olefin polymerization according to the above 1),wherein Mt is Al, B, Zn or Be

3) A catalyst for olefin polymerization according to the above 1) or 2),wherein α and β satisfy the relationship α>0 and 0.5≦β/α<10.

4) A catalyst for olefin polymerization according to any of the above 1)to 3), wherein R¹ is a primary alkyl group.

5) A catalyst for olefin polymerization according to any of the above 1)to 4), wherein the compound [B] of a transition metal selected frommetals of Groups 3-11 of the Periodic Table is a compound represented bythe following formula (1):L_(j)W_(k)MX_(p)X′_(q)  (1)wherein L denotes a η-bonding cyclic anion ligand selected independentlyfrom the group consisting of a cyclopentadienyl group, indenyl group,tetrahydroindenyl group, fluorenyl group, tetrahydrofluorenyl group andoctahydrofluorenyl group, and the ligand may optionally have 1-8substituents, and the substituent(s) is (are) substituent(s) having 20or less non-hydrogen atoms which is (are) independently selected fromthe group consisting of hydrocarbon groups of 1-20 carbon atoms, halogenatoms, halogen-substituted hydrocarbon groups of 1-12 carbon atoms,aminohydrocarbyl groups of 1-12 carbon atoms, hydrocarbyloxy groups of1-12 carbon atoms, dihydrocarbylamino groups of 1-12 carbon atoms,hydrocarbylphosphino groups of 1-12 carbon atoms, silyl groups,aminosilyl groups, hydrocarbyloxysilyl groups of 1-12 carbon atoms, andhalosilyl groups;

M denotes a transition metal having a formal oxidation number of +2, +3or +4 which is selected from the group consisting of the transitionmetals belonging to Group 4 of the Periodic Table and is η⁵-bonded to atleast one ligand L;

W is a divalent substituent having 50 or less non-hydrogen atoms andbonded monovalently to L and M, respectively, thereby to form ametallo-cycle together with L and M;

X denotes an anionic σ-bonding type ligand having 60 or lessnon-hydrogen atoms which is selected independently from the groupconsisting of monovalent anionic σ-bonding type ligands, divalentanionic σ-bonding type ligands divalently bonded to M and divalentanionic σ-bonding type ligands bonded monovalently to L and Mrespectively;

X′ denotes independently a neutral Lewis base coordinate compound having40 or less non-hydrogen atoms;

j is 1 or 2, with a proviso that in the case of j being 2, the twoligands L may optionally bond to each other through a divalent grouphaving 20 or less non-hydrogen atoms, and the divalent group is selectedfrom the group consisting of hydrocarbadiyl groups of 1-20 carbon atoms,halohydrocarbadiyl groups of 1-12 carbon atoms, hydrocarbyleneoxy groupsof 1-12 carbon atoms, hydrocarbyleneamino groups of 1-12 carbon atoms,silanediyl groups, halosilanediyl groups, and silyleneamino groups;

k is 0 or 1; and

p is 0, 1 or 2, with a proviso that in the case of X being a monovalentanionic σ-bonding type ligand or a divalent anionic σ-bonding typeligand bonded to L and M, p is an integer which is smaller by at least 1than the formal oxidation number of M, and in the case of X being adivalent anionic σ-bonding type ligands bonded only to M, p is aninteger which is smaller by at least (j+1) than the formal oxidationnumber of M, and q is 0, 1 or 2.

6) A catalyst for olefin polymerization according to any of the above 1)to 5), wherein the activator compound (C-1) capable of reacting with thetransition metal compound [B] to form a metal complex having catalyticactivity is a compound represented by the following formula (2):[L−H]^(d+)[M_(m)Q_(p)]^(d−)  (2)wherein [L−H]^(d+) denotes a proton donating Brφnsted acid, L denotes aneutral Lewis base, and d is an integer of 1-7; [M_(m)Q_(p)]^(d−)denotes a compatible non-coordination anion, M denotes a metal ormetalloid belonging to Groups 5-15 of the Periodic Table, Q is selectedindependently from the group consisting of hydrides, halides,dihydrocarbylamido groups of 2-20 carbon atoms, hydrocarbyloxy groups of1-30 carbon atoms, hydrocarbon groups of 1-30 carbon atoms andsubstituted hydrocarbon groups of 1-40 carbon atoms, the number of Q,which is a halide, is 1 or less, m is an integer of 1-7, p is an integerof 2-14, d is as defined above, and p−m=d).

7) A method for production of polyolefins, comprising polymerizing orcopolymerizing olefins in the presence of the catalyst for olefinpolymerization according to any of the above 1) to 6).

According to one embodiment of the present invention, catalysts forolefin polymerization are provided, comprising a solid catalystcomponent comprising [A] a solid component having substantially nohydroxyl group, [B] a compound of a transition metal selected fromGroups 3-11 of the Periodic Table, and [C] a mixture of an activatorcompound (C-1) capable of reacting with the transition metal compound[B] to form a metal complex having catalytic activity and anorganoaluminum compound (C-2); and [D] a specific organomagnesiumcompound.

Such catalysts for olefin polymerization have high activity, and theorganomagnesium compound used therein as a scavenger displays a highpolymerization activity in a wide range of concentration. When thecatalyst for olefin polymerization of the present invention is used forpolymerization of ethylene, ethylene polymers having excellent particleproperties, such as fluidity and packing density, can be obtained.Therefore, stirring in the reaction vessel can be efficiently performedand the polymerization heat can be effectively removed, wherebyimprovement of productivity can be expected.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described in detail.

The solid component [A] having substantially no hydroxyl group used inthe present invention can be obtained by subjecting a solid material(hereinafter referred to as “precursor of component [A]”) to a treatmentfor removing hydroxyl groups from the surface of the precursor of thecomponent [A].

Examples of the precursor of the component [A] include porous polymericmaterials (the matrix including polyolefins or modified products thereofsuch as polyethylene, polypropylene, polystyrene, ethylenepropylenecopolymer, ethylene-vinyl ester copolymer, styrene-divinylbenzenecopolymer, partial or complete saponification products of ethylene-vinylester copolymer, thermoplastic resins such as polyamides, polycarbonatesand polyesters, theremosetting resins such as phenolic resins, epoxyresins and melamine resins, etc.), inorganic solid oxides of elementsbelonging to Groups 2-4, 13 or 14 of the Periodic Table (e.g., silica,alumina, magnesia, magnesium chloride, zirconia, titania, boron oxide,calcium oxide, zinc oxide, barium oxide, vanadium pentoxide, chromiumoxide, thorium oxide, and mixtures thereof or composite oxides thereof).Examples of composite oxides containing silica include composite oxidesof silica with oxides of elements selected from those belonging to Group2 or 13 of the Periodic Table, such as silica-magnesia andsilica-alumina. In the present invention, the precursors of thecomponent [A] are preferably selected from silica, alumina and compositeoxides of silica with oxides of elements selected from those belongingto Group 2 or 13 of the Periodic Table. Of these inorganic solid oxides,silica is especially preferred.

The form of the silica products used as the precursors of the component[A] is not particularly limited, and they may be in any form, such asgranule, sphere, aggregate, fume, etc. Preferred examples ofcommercially available silica products include SD3216.30, SP-9-10046,Davison Syloid TM 245, Davison 948 or Davison 952 [all of them beingmanufactured by Grace Davison Co. Ltd. (division of W.R. Davison Co.Ltd. (USA))], Aerosil 812 (manufactured by Degussa AG (Germany)), ES70X(manufactured by Crossfield Co. Ltd. (USA)), P-6 and P-10 (manufacturedby Fuji Silicia Co., Ltd. (Japan)), etc.

The specific surface area of the component [A] used in the presentinvention obtained by a nitrogen gas adsorption method according toB.E.T. (Brunauer-Emmett-Teller) is preferably 10-1000 m²/g, morepreferably 100-600 m²/g. One of the representative examples of thecomponent [A] having such a high specific surface area is a componentcomprising a porous material having a number of pores.

The pore volume of the component [A] obtained by the nitrogen gasadsorption method in the present invention is preferably not more than 5cm³/g, more preferably 0.1-3 cm³/g, and further preferably 0.2-2 cm³/g.

The average particle diameter of the component [A] used in the presentinvention is not particularly limited. The average particle diameter ofthe component [A] is preferably 0.5-500 μm, more preferably 1-200 μm,and further preferably 10-100 μm.

The component [A] having substantially no hydroxyl group in the presentinvention can be obtained by subjecting the precursor of the component[A] to a chemical treatment to remove hydroxyl groups from the surfaceof the precursor of the component [A].

“Solid component has substantially no hydroxyl group” in the presentinvention means that hydroxyl groups are not detected on the surface ofthe solid component [A] by the following method (i) or (ii).

In the method (i), a given excess amount of dialkylmagnesium is added toa slurry obtained by dispersing the component [A] in a solvent to allowthe hydroxyl groups on the surface of the component [A] to react withthe dialkylmagnesium, then the amount of unreacted dialkylmagnesiumremaining in the solvent is measured by a known method in order toobtain the amount of the dialkylmagnesium which has reacted with thehydroxyl groups on the surface of the component [A], and then theinitial amount of the hydroxyl groups on the surface of the component[A] is obtained based on the amount of the reacted dialkylmagnesium.This method is based on the reaction of hydroxyl groups withdialkylmagnesium shown by the following reaction formula.S—OH+MgR₂→S—OMgR+RH(in the formula, S denotes the solid material (the component [A]) and Rdenotes an alkyl group).

In the method (ii) which is preferred to the method (i),ethoxydiethylaluminum is used in place of the dialkylmagnesium.Specifically, in the method (ii), ethoxydiethylaluminum is reacted withhydroxyl groups on the surface of the component [A] to produce ethanegas, and the amount of the produced ethane gas is measured by a gasburette, and then the initial amount of hydroxyl group on the surface ofthe component [A] is obtained based on the amount of the produced ethanegas.

Furthermore, in the present invention, it is preferred to heat-treat theprecursor of the component [A], thereby removing water (crystal water,adsorbed water, etc.). The heat treatment of the precursor of thecomponent [A] can be carried out, for example, in an inert atmosphere ora reducing atmosphere at a temperature of preferably 150-1000° C., morepreferably 250-800° C. for 1-50 hours.

In the present invention, more preferably, after the removal of water bythe heat-treatment, the precursor of the component [A] is furthersubjected to a chemical treatment to remove a part or all of thehydroxyl groups from the surface of the precursor of the component [A],thereby obtaining the component [A].

The chemical treatment for removing a part or all of the hydroxyl groupsfrom the precursor of the component [A] is desirably a chemicaltreatment which comprises contacting the precursor of the component [A]with an organometallic compound. Examples of the organometallic compoundused for this chemical treatment are compounds of the elements belongingto Groups 2-13 of the Periodic Table, and the like. Of these compounds,especially preferred are organoaluminum compounds or organomagnesiumcompounds.

Examples of preferred organoaluminum compounds used for the chemicaltreatment of the precursor of the component [A] include compoundsrepresented by the following formula (3).AlR_(n)X_(3-n)  (3)(in the formula, R denotes independently a straight chain, branchedchain or cyclic alkyl group of 1-12 carbon atoms or an aryl group of6-20 carbon atoms, X denotes independently a halide, a hydride or analkoxide group of 1-10 carbon atoms, and n is a real number of more than0 and not more than 3).

The compounds represented by the above formula (3) may be used alone orin combination of two or more. Examples of the group R in the formula(3) include a methyl group, ethyl group, propyl group, butyl group,hexyl group, octyl group, decyl group, phenyl group, tolyl group, etc.

Examples of the group X in the formula (3) include a methoxy group,ethoxy group, butoxy group, hydrogen atom, chlorine atom, etc.

Examples of the organoaluminum compounds used for the chemical treatmentof the precursor of the component [A] include trialkylaluminum compoundssuch as trimethylaluminum, triethylaluminum, tributylaluminum,trihexylaluminum, trioctylaluminum and tridecylaluminum, and reactionproducts of these trialkylaluminum compounds with alcohols (e.g., methylalcohol, ethyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol,octyl alcohol, decyl alcohol, etc.).

Examples of the reaction products include methoxydimethylaluminum,ethoxydiethylaluminum, butoxydibutylaluminum, etc. In the production ofthese reaction products, the ratio of the trialkylaluminum to thealcohol in molar ratio of Al/OH is in the range of preferably 0.3-20,more preferably 0.5-5, further preferably 0.8-3.

Examples of preferred organomagnesium compounds used for the chemicaltreatment of the precursor of the component [A] include compoundsrepresented by the following formula (4).MgR_(n)X_(2-n)  (4)(in the formula, R denotes independently a straight chain, branchedchain or cyclic alkyl group of 1-12 carbon atoms or an aryl group of6-20 carbon atoms, X denotes independently a halide, a hydride or analkoxide group of 1-10 carbon atoms, and n is 1 or 2).

The compounds represented by the above formula (4) may be used alone orin combination of two or more.

Examples of the group R in the formula (4) include a methyl group, ethylgroup, n-propyl group, isopropyl group, n-butyl group, isobutyl group,sec-butyl group, tert-butyl group, pentyl group, hexyl group, octylgroup, decyl group, phenyl group, tolyl group, etc.

Examples of the group X in the formula (4) include a methoxy group,ethoxy group, butoxy group, hydrogen atom, chlorine atom, etc.

Examples of the organomagnesium compounds used for the chemicaltreatment of the precursor of the component [A] includedi-sec-butylmagnesium, n-butylethylmagnesium, n-butyl-n-octylmagnesium,etc.

In the chemical treatment of the precursor of the component [A], theabove organoaluminum compound and organomagnesium compound may be usedin admixture.

In the case of obtaining the component [A] by the chemical treatment ofthe precursor of the component [A], the organometallic compound is usedin an amount equal to or larger than the molar amount of the hydroxylgroups present on the surface of the precursor of the component [A]. Theamount of the organometallic compound used for the chemical treatment ispreferably 1-10 times, more preferably 1-5 times, further preferably 1-2times, especially preferably 1-1.5 times, most preferably 1-1.3 timesthe molar amount of the hydroxyl groups present on the surface of theprecursor of the component [A].

Moreover, in the present invention, the component [A] is especiallypreferably a silica having substantially no hydroxyl group. The silicais preferably one obtained by a method which comprises heat-treatingsilica at a temperature of preferably not lower than 150° C., morepreferably not lower than 250° C., to have the amount of hydroxyl groupson the surface being 0.05-10 mmols per 1 g of silica and treating thethus pretreated silica with an organometallic compound. As theorganometallic compound used for the treatment of silica (precursor ofthe component [A]), an organoaluminum compound is preferred, and theorganoaluminum compound of the formula (3) is especially preferred. Theamount of the organoaluminum compound to be used is preferably 1-10times the molar amount of the hydroxyl groups on the surface of thepretreated silica.

The amount of the hydroxyl groups on the surface of the pretreatedsilica is more preferably 0.1-5 mmols, most preferably 0.5-2 mmols per 1g of the pretreated silica.

In addition, clays, clay minerals and ion-exchangeable laminar compoundstreated with organoaluminum compounds which are mentioned hereafter asexamples of the component [C] can also be used as the component [A].

Next, the compound [B] which is a compound of a transition metalselected from Groups 3-11 of the Periodic Table will be described below.

As examples of the component [B] used in the present invention, thecompounds represented by the following formula (1) are included:L_(j)W_(k)MX_(p)X′_(q)  (1)(in the formula, L denotes independently a η-bonding type cyclic anionligand selected from the group consisting of cyclopentadienyl group,indenyl group, tetrahydroindenyl group, fluorenyl group,tetrahydrofluorenyl group and octahydrofluorenyl group, and, the ligandoptionally may have 1-8 substituents, and the substituents are thosehaving 20 or less non-hydrogen atoms which are independently selectedfrom hydrocarbon groups of 1-20 carbon atoms, halogen atoms,halogen-substituted hydrocarbon groups of 1-12 carbon atoms,aminohydrocarbyl groups of 1-12 carbon atoms, hydrocarbyloxy groups of1-12 carbon atoms, dihydrocarbylamino groups of 1-12 carbon atoms,hydrocarbylphosphino groups of 1-12 carbon atoms, silyl groups,aminosilyl groups, hydrocarbyloxysilyl groups of 1-12 carbon atoms andhalosilyl groups,

M denotes a transition metal having a formal oxidation number of +2, +3or +4 which is selected from the group of the transition metalsbelonging to Group 4 of the Periodic Table and is η⁵-bonded to at leastone ligand L,

W is a divalent substituent having 50 or less non-hydrogen atoms andbonded monovalently to L and M, respectively, thereby to form ametallo-cycle together with L and M,

X denotes an anionic σ-bonding type ligand having 60 or lessnon-hydrogen atoms which is selected from the group consisting ofmonovalent anionic σ-bonding type ligands, divalent anionic σ-bondingtype ligands bonded divalently to M and divalent anionic σ-bonding typeligands bonded monovalently to L and M, respectively,

X′ denotes independently a neutral Lewis base coordination compoundhaving 40 or less non-hydrogen atoms,

j is 1 or 2, with a proviso that in the case of j being 2 two ligands Lmay optionally bond to each other through a divalent group having 20 orless non-hydrogen atoms, and the divalent group is selected from thegroup consisting of hydrocarbadiyl groups of 1-20 carbon atoms,halohydrocarbadiyl groups of 1-12 carbon atoms, hydrocarbyleneoxy groupsof 1-12 carbon atoms, hydrocarbyleneamino groups of 1-12 carbon atoms,silanediyl groups, halosilanediyl groups, and silyleneamino groups,

k is 0 or 1, and

p is 0, 1 or 2, with a proviso that in the case of X being a monovalentanionic σ-bonding type ligand or a divalent anionic σ-bonding typeligand bonded to L and M, p is an integer which is smaller by at least 1than the formal oxidation number of M, and in the case of X being adivalent anionic σ-bonding type ligand bonded to only M, p is an integerwhich is smaller by at least (j+1) than the formal oxidation number ofM, and q is 0, 1 or 2).

Examples of the ligand X in the compound of the above formula (1)include hydrides, halides, hydrocarbon groups of 1-60 carbon atoms,hydrocarbyloxy groups of 1-60 carbon atoms, hydrocarbylamide groups of1-60 carbon atoms, hydrocarbylphosphide groups of 1-60 carbon atoms,hydrocarbylsulfide groups of 1-60 carbon atoms, silyl groups, compositegroups of these groups, etc.

Examples of the neutral Lewis base coordination compound X′ in thecompound of the above formula (1) are phosphines, ethers, amines,olefins of 2-40 carbon atoms, dienes of 1-40 carbon atoms, divalentgroups derived from these compounds, etc.

As examples of the component [B] used in the present invention, thecomplex compounds represented by the following formula (5) are included:

(in the formula, R¹ and R⁴ denote independently of one another analiphatic hydrocarbon group of 1-20 carbon atoms or an aromatic group of7-20 carbon atoms in total having a hydrocarbon group(s) on the ring, R²and R³ denote independently of one another a hydrogen atom or ahydrocarbon group of 1-20 carbon atoms, and R² and R³ may bond to eachother to form a ring, X and Y denote independently of one another ahalogen atom or a hydrocarbon group of 1-20 carbon atoms, and M denotesnickel or palladium).

The aliphatic hydrocarbon groups of 1-20 carbon atoms of R¹ and R⁴ inthe above formula (5) include a straight chain or branched chain alkylgroup of 1-20 carbon atoms, a cycloalkyl group of 3-20 carbon atoms,etc., and more specifically a methyl group, ethyl group, n-propyl group,isopropyl group, n-butyl group, isobutyl group, sec-butyl group,tert-butyl group, pentyl group, hexyl group, octyl group, decyl group,tetradecyl group, hexadecyl group, octadecyl group, cylopentyl group,cyclohexyl group, cyclooctyl group, etc. The ring of the cycloalkylgroup may have a suitable substituent such as a lower alkyl group.

Examples of the aromatic groups of 7-20 carbon atoms in total having ahydrocarbon group(s) on the ring are a phenyl group, naphthyl group,etc. having on the aromatic ring one or more straight chain, branchedchain or cyclic alkyl groups of 1-10 carbon atoms. As R¹ and R⁴,aromatic groups having a hydrocarbon group(s) on the ring and especiallythe 2,6-diisopropylphenyl group, are preferred. R¹ and R⁴ may be thesame or different.

Examples of the hydrocarbon group of 1-20 carbon atoms of R² and R³include straight chain or branched chain alkyl groups of 1-20 carbonatoms, cycloalkyl groups of 3-20 carbon atoms, aryl groups of 6-20carbon atoms, aralkyl groups of 7-20 carbon atoms, etc. Examples of thestraight chain or branched chain alkyl groups of 1-20 carbon atoms andcycloalkyl groups of 3-20 carbon atoms include the same groups as listedfor the examples of the aliphatic hydrocarbon group of 1-20 carbon atomsof the above R¹ and R⁴. Examples of the aryl groups of 6-20 carbon atomsinclude a phenyl group, tolyl group, xylyl group, naphthyl group,methylnaphthyl group, etc, and the examples of the aralkyl groups of7-20 carbon atoms include a benzyl group, phenethyl group, etc.

R² and R³ may be the same or different. They also may bond to each otherto form a ring. Examples of the halogen atoms of X and Y includechlorine, bromine, iodine atoms, etc., and the examples of thehydrocarbon groups of 1-20 carbon atoms of X and Y include the same aslisted for the examples of the hydrocarbon groups of 1-20 carbon atomsof the above R² and R³. As X and Y, a bromine atom or methyl group ispreferred. X and Y may be the same or different.

In addition, as examples of the component [B] used in the presentinvention, complexes of the compounds represented by the followingformula (6) with nickel compounds may be mentioned:

(in the formula, R¹, R², R³ and R⁴ denote independently of one another astraight chain, branched chain or cyclic alkyl group of 1-12 carbonatoms, an aryl group of 6-20 carbon atoms, hydrogen or a vinyl group).

Examples of the nickel compounds includebis(1,5-cyclooctadiene)nickel(0), bis(cyclooctatetraene)nickel(0),tetracarbonyl-nickel(0), bis(acetylacetonato)nickel(II), nickelacetate(II), bis(allyl)nickel(II), etc.

In the present invention, the transition metal compounds represented bythe above formula (1) (j=1) are preferred as the component [B].

As preferred examples of the compounds represented by the formula (1)(j=1), the compounds represented by the following formula (7) areincluded:

(in the formula, M denotes a transition metal selected from the groupconsisting of titanium, zirconium and hafnium and having a formaloxidation number of +2, +3 or +4,

R⁵ denotes a substituent having 20 or less non-hydrogen atoms which isindependently selected from the group consisting of hydrogen atoms,hydrocarbon groups of 1-8 carbon atoms, silyl groups, germyl groups,cyano groups, halogen atoms and composite groups thereof, with a provisothat when the substituent R⁵ is a hydrocarbon group of 1-8 carbon atoms,a silyl group or germyl group, the two adjacent substituents R⁵ may bondto each other to form a divalent group, thereby to form a ring togetherwith a bond between two carbon atoms of the cyclopentadienyl ring whichrespectively bond to the two adjacent substituents R⁵,

X″ denotes a substituent having 20 or less non-hydrogen atoms which isindependently selected from the group consisting of hydrides, halides,hydrocarbon groups of 1-20 carbon atoms, hydrocarbyloxy groups of 1-18carbon atoms, hydrocarbylamino groups of 1-18 carbon atoms, silyl group,hydrocarbylamide groups of 1-18 carbon atoms, hydrocarbylphosphidegroups of 1-18 carbon atoms, hydrocarbylsulfide groups of 1-18 carbonatoms, and composite groups of these groups, and the two substituents X″optionally may form together a neutral conjugated diene of 4-30 carbonatoms or a divalent group,

Y′ denotes —O—, —S—, —NR*— or —PR*—, in which R* denotes a hydrogenatom, a hydrocarbon group of 1-12 carbon atoms, a hydrocarbyloxy groupof 1-8 carbon atoms, silyl group, a halogenated alkyl group of 1-8carbon atoms, a halogenated aryl group of 6-20 carbon atoms or acomposite group thereof, and

Z denotes SiR*₂, CR*₂, SiR*₂SiR*₂, CR*₂CR*₂, CR*═CR*, CR*₂SiR*₂ orGeR*₂, in which R* is as defined above, and n is 1, 2 or 3).

Examples of the component [B] used in the present invention arecompounds as listed below.

Bis(cyclopentadienyl)methylzirconium hydride,bis(cyclopentadienyl)ethylzirconium hydride,bis(cyclopentadienyl)phenylzirconium hydride,bis(cyclopentadienyl)benzylzirconium hydride,bis(cyclopentadienyl)neopentylzirconium hydride,bis(methylcyclopentadienyl)zirconium dimethyl,bis(n-butylcyclopentadienyl)zirconium dimethyl, bis(indenyl)zirconiumdimethyl, (pentamethylcyclopentadienyl)(cyclopentadienyl)zirconiumdimethyl, bis(cyclopentadienyl)zirconium dimethyl,bis(pentamethylcyclopentadienyl)zirconium dimethyl,bis(cyclopentadienyl)zirconium diphenyl, bis(cyclopentadienyl)zirconiumdibenzyl, bis(cyclopentadienyl)zirconium dihydride,bis(fluorenyl)zirconium dimethyl, ethylene-bis(indenyl)zirconiumdimethyl, ethylene-bis(indenyl)zirconium diethyl,ethylene-bis(indenyl)zirconium dihydride,ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dimethyl,ethylenebis(4-methyl-1-indenyl)zirconium dimethyl,ethylenebis(5-methyl-1-indenyl)zirconium dimethyl,ethylenebis(6-methyl-1-indenyl)zirconium dimethyl,ethylenebis(7-methyl-1-indenyl)zirconium dimethyl,ethylenebis(5-methoxy-1-indenyl)zirconium dimethyl,ethylenebis(2,3-dimethyl-1-indenyl)zirconium dimethyl,ethylenebis(4,7-dimethyl-1-indenyl)dimethylzirconium,ethylenebis(4,7-dimethoxy-1-indenyl)zirconium dimethyl,methylene-bis(cyclopentadienyl)zirconium dihydride,methylene-bis(cyclopentadienyl)zirconium dimethyl,isopropylidene(cyclopentadienyl)zirconium dihydride,isopropylidene(cyclopentadienyl)zirconium dimethyl,isopropylidene(cyclopentadienyl-fluorenyl)zirconium dihydride,isopropylidene(cyclopentadienyl-fluorenyl)zirconium dimethyl,silylenebis(cyclopentadienyl)zirconium dihydride,silylenebis(cyclopentadienyl)zirconium dimethyl,dimethylsilylene(cyclopentadienyl)zirconium dihydride,dimethylsilylene(cyclopentadienyl)zirconium dimethyl,[(N-t-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyl]titaniumdimethyl, [(N-t-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-dimethylsilane]titanium dimethyl,[(N-methylamido)-(tetramethyl-η⁵-cyclopentadienyl)dimethylsilane]titaniumdimethyl,[(N-phenylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilane]titaniumdimethyl,[(N-benzylamido)(tetramethyl-η⁵-cyclopentadienyl)-dimethylsilane]titaniumdimethyl, [(N-t-butylamido)(η⁵-cyclopentadienyl)-1,2-ethanediyl]titaniumdimethyl, [(N-t-butylamido) (5-cyclopentadienyl)dimethylsilane]-titaniumdimethyl, [(N-methylamido) (η⁵-cyclopentadienyl)-1,2-ethanediyl]titaniumdimethyl, [(N-methylamido)(η⁵-cyclopentadienyl)dimethylsilane]-titaniumdimethyl, [(N-t-butylamido)(η⁵-indenyl)-dimethylsilane]titaniumdimethyl, [(N-benzylamido) (η⁵-indenyl)dimethylsilane]titanium dimethyl,etc.

Additional examples of the component [B] used in the present inventioninclude compounds having the names obtained by replacing the portion of“dimethyl” in the above-listed zirconium and titanium compounds (whichis the last portion of the names of the compounds, namely, which appearsjust behind the portion “zirconium” or “titanium” and which correspondsto the portion of “X″” in the above formula (7)) with any of thoseenumerated below.

“dibenzyl”, “2-(N,N-dimethylamino)benzyl”, “2-butene-1,4-diyl”,“s-trans-η⁴-1,4-diphenyl-1,3-butadiene”,“s-trans-η⁴-3-methyl-1,3-pentadiene”,“S-trans-η⁴-1,4-dibenzyl-1,3-butadiene”, “s-trans-η⁴-2,4-hexadiene”,“s-trans-η⁴-1,3-pentadiene”, “s-trans-η⁴-1,4-ditolyl-1,3-butadiene”,“s-trans-η⁴-1,4-bis(trimethylsilyl)-1,3-butadiene”,“s-cis-η⁴-1,4-diphenyl-1,3-butadiene”,“s-cis-η⁴-3-methyl-1,3-pentadiene”,“s-cis-η⁴-1,4-dibenzyl-1,3-butadiene”, “s-cis-η⁴-2,4-hexadiene”,“s-cis-η⁴-1,3-pentadiene”, “s-cis-η⁴-1,4-ditolyl-1,3-butadiene”,“s-cis-η⁴-1,4-bis(trimethylsilyl)-1,3-butadiene”, etc.

The transition metal compound [B] used in the present invention can besynthesized by generally known methods. Examples of the preferredmethods for synthesis of the transition metal compounds used as thecomponent [B] in the present invention include that disclosed in U.S.Pat. No. 5,491,246.

The transition metal compound component [B] may be used alone or incombination.

The mixture [C] used as one component of the catalyst of the presentinvention (hereinafter sometimes referred to as “component [C]”) will bedescribed below. The component [C] is a mixture of the followingcompounds.

(C-1) An activator compound capable of reacting with the transitionmetal compound [B] to form a metal complex having catalytic activity;

(C-2) An organoaluminum compound.

As the component (C-1), for example, a compound defined by the followingformula (8) is included:[L−H]^(d+)[M_(m)Q_(p)]^(d−)  (8)In the above formula, [L−H]d⁺ denotes a proton donating Brφnsted acid,and L denotes a neutral Lewis base.

In the above formula, [M_(m)Q_(p)]^(d−) denotes a compatiblenon-coordination anion, M denotes a metal or metalloid selected fromGroups 5-15 of the Periodic Table, Q is independently a hydride, adialkylamide group, a halide, an alkoxide group, an aryloxide group, ahydrocarbon group, or a substituted hydrocarbon group of 20 or lesscarbon atoms, and the number of Q, which is a halide, is 1 or less, m isan integer of 1-7, p is an integer of 2-14, d is an integer of 1-7, andp−m=d.

In the present invention, preferred examples of the component (C-1) arethose represented by the following formula (9):[M_(m)Q_(n)](G_(q)(T−H))_(z)]^(d−)  (9)

In the above formula, M is a metal or metalloid selected from Groups5-15 of the Periodic Table.

Q is as defined in the formula (8), G is a polyvalent hydrocarbon groupbonding to boron and T and having a valence of r+1, T is O, S, NR or PRwhere R is a hydrocarbyl group, trihydrocarbylsilyl group,trihydrocarbylgermanium group or hydrogen, and

m is an integer of 1-7, n is an integer of 0-7, q is an integer of 0 or1, r is an integer of 0-3, z is an integer of 1-8, d is an integer of1-7, and n+z−m=d.

More preferred examples of the component (C-1) are those which arerepresented by the following formula (10):[L−H]⁺[BQ₃Q′]⁻  (10)

In the above formula, [L−H]⁺ is a proton donating Brφnsted acid, and Lis a neutral Lewis base, [BQ₃Q′]⁻ is a compatible non-coordinationanion, Q is a pentafluorophenyl group, and the group Q′ is a substitutedaryl group of 6-20 carbon atoms having one OH group as a substituent.

Examples of the compatible non-coordination anions in the presentinvention are tetrakisphenyl borate, tri(p-tolyl)(phenyl) borate,tris(pentafluorophenyl)(phenyl) borate,tris(2,4-dimethylphenyl)(hydroxyphenyl) borate,tris(3,5-dimethylphenyl)(phenyl) borate,tris(3,5-di-trifluoromethylphenyl)(phenyl)borate,tris(pentafluorophenyl)(cyclohexyl)borate,tris(pentafluorophenyl)-(naphthyl) borate, tetrakis(pentafluorophenyl)borate, triphenyl(hydroxyphenyl) borate, diphenyl-di(hydroxyphenyl)borate, triphenyl(2,4-dihydroxyphenyl) borate,tri(p-tolyl)(hydroxyphenyl) borate,tris(pentafluorophenyl)(hydroxyphenyl) borate,tris(2,4-dimethylphenyl)(hydroxyphenyl) borate,tris(3,5-dimethylphenyl)(hydroxyphenyl) borate,tris(3,5-di-trifluoromethylphenyl)(hydroxyphenyl) borate,tris(pentafluorophenyl)(2-hydroxyethyl) borate,tris(pentafluorophenyl)(4-hydroxybutyl) borate,tris(pentafluorophenyl)(4-hydroxy-cyclohexyl) borate,tris(pentafluorophenyl)(4-(4′-hydroxyphenyl)phenyl) borate,tris(pentafluorophenyl)(6-hydroxy-2-naphthyl) borate, etc. The mostpreferred is tris(pentafluorophenyl)(4-hydroxyphenyl) borate.

Other examples of the preferred compatible non-coordination anionsinclude the above enumerated borates in which the hydroxyl group isreplaced with an NHR group, wherein R is preferably a methyl group,ethyl group or tert-butyl group. Examples of the proton donatingBrφnsted acids include trialkyl group-substitution type ammonium cationssuch as triethylammonium, tripropylammonium, tri(n-butyl)ammonium,trimethylammonium, tributylammonium and tri(n-octyl)ammonium. Moreover,N,N-dialkylanilinium cations such as N,N-dimethylanilinium,N,N-diethylanilinium, N,N-2,4,6-pentamethylanilinium andN,N-dimethylbenzylanilinium are also suitable.

Further, dialkylammonium cations such as di-(i-propyl)ammonium anddicyclohexylammonium are also suitable, and triarylphosphonium cationssuch as triphenylphosphonium, tri(methylphenyl)phosphonium andtri(dimethylphenyl)phosphonium, or dimethylsulfonium, diethylsulfonium,diphenylsulfonium, etc. are also suitable.

In addition, as the component (C-1), for example, clays, clay mineralsor ion-exchangeable laminar compounds are included.

The clays used in the present invention are preferably those which aremainly composed of clay minerals, and the ion-exchangeable laminarcompounds are preferably those which have a crystal structure in whichthe planes formed by ionic bonding or the like are stacked in parallelwith each other by a weak bonding force and have exchangeable ions. Asexamples of the clays, clay minerals or ion-exchangeable laminarcompounds, ion crystalline compounds having laminar crystal structuressuch as hexagonal close packing type, antimony type, CdCl₂ type and CdI₂type, etc. are included. These clays, clay minerals or ion-exchangeablelaminar compounds are not limited to natural ones, but includeartificially synthesized products.

Examples of the clays and clay minerals include kaolin, bentonite,kibushi-clay, gairome-clay, allophane, hisingerite, pyrophyllite, micagroup, montmorillonite group, vermiculite, chlorite group, palygorskite,kaolinite, nacrite, dickite, halloysite, etc. Examples of theion-exchangeable laminar compounds include crystalline acidic salts ofpolyvalent metals, such as α-Zr(HAsO₄)₂.H₂O, α-Zr(HPO₄)₂,α-Zr(KPO₄)₂.3H₂O, α-Ti(HPO₄)₂, α-Ti(HAsO₄)₂.H₂O, α-Sn(HPO₄)₂.H₂O,γ-Zr(HPO₄)₂, γ-Ti(HPO₄)₂, and γ-Ti(NH₄PO₄)₂.H₂O.

These clays, clay minerals or ion-exchangeable laminar compoundspreferably have a pore volume of pores of 2 nm or more in radiusmeasured by the mercury penetration method of not less than 0.1 cm³/g,especially preferably 0.3-5 cm³/g, from the view-point of polymerizationactivity. The measurement of the pore volume is conducted by the mercurypenetration method in the range of 2-3×10² nm in pore radius using amercury porosimeter.

The clays and clay minerals used in the present invention can besubjected to a chemical treatment. As the chemical treatment, either asurface treatment to remove impurities adhered to the surfaces or atreatment to affect their crystalline structure is used. Specifically,the treatments include acid treatment, alkali treatment, salt treatment,organic material treatment, etc. The acid treatment removes theimpurities on the surface and, in addition, dissolves out the cationssuch as Al, Fe and Mg in the crystal structure, thereby increasing thesurface area. By the alkali treatment, the crystalline structure of theclay is broken, resulting in a change of the structure of the clay.Moreover, by the salt treatment and organic material treatment, ioncomposites, molecule composites, organic derivatives, etc. are formed,and the surface area and interlaminar distance can be changed.

The ion-exchangeable laminar compounds used in the present invention maybe the laminar compounds in the state where the interlaminar distancesare enlarged by exchanging the interlaminar exchangeable ions with otherlarge and bulky ions by taking advantage of the ion-exchanging ability.Here, the bulky ions play a role of props supporting the laminarstructure, and are called pillars. Furthermore, introduction of anothersubstance (guest compound) between the layers of a laminar substance iscalled intercalation.

Examples of the guest compounds to be intercalated include cationicinorganic compounds such as TiCl₄ and ZrCl₄; metal alcoholates such asTi(OR)₄, Zr(OR)₄, PO(OR)₃ and B(OR)₃ (R is a hydrocarbon group, etc.);metal hydroxide ions such as [Al₁₃O₄(OH)₂₄]⁷⁺, [Zr₄(OH)₁₄]²⁺ and[Fe₃O(OCOCH₃)₆]⁺; etc. These compounds may be used either alone or in acombination of two or more.

Furthermore, upon intercalating these compounds, a polymer obtained byhydrolyzing metal alcoholates such as Si(OR)₄, Al(OR)₃ and Ge(OR)₄ (R isa hydrocarbon group, etc.), etc., or colloidal inorganic compounds suchas SiO₂, etc. may be present at the same time. Other examples of thepillars include oxides produced by intercalating the above hydroxideions between layers, followed by dehydrating by heating.

The clays, clay minerals or ion-exchangeable laminar compounds used inthe present invention may be used as they are or may be used aftersubjecting them to grinding by a ball mill or screening. Furthermore,they may be used after adding and adsorbing water or after a dehydrationtreatment by heating. They may be used either alone or in combination oftwo or more. Among them, preferred are clays or clay minerals, andespecially preferred is montmorillonite.

In the present invention, these activator compound components (C-1) maybe used either alone or in combination.

Next, the organoaluminum compound (C-2) used in the present inventionwill be described. Examples of the component (C-2) of the presentinvention include trimethylaluminum, triethylaluminum, tributylaluminum,trihexylaluminum, trioctylaluminum, tridecylaluminum, etc. and thereaction products of these alkylaluminums with alcohols such as methylalcohol, ethyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol,octyl alcohol and decyl alcohol, for example, dimethylmethoxyaluminum,diethylethoxyaluminum and dibutylbutoxyaluminum, etc.

In the production of these reaction products, the ratio of thealkylaluminum and the alcohol, namely, Al/OH, is in the range ofpreferably 0.3-20, more preferably 0.5-5, further preferably 0.8-3.

In the present invention, the amount of the component (C-2) is 0.01-1000times, preferably 0.1-100 times, more preferably 0.5-10 times the molaramount of the component (C-1).

The reaction of the component (C-1) with the component (C-2) is carriedout between room temperature and 150° C. in an inert reaction medium,for example, aliphatic hydrocarbons such as hexane and heptane andaromatic hydrocarbons such as benzene and toluene. As for the sequenceof the reactions, any of a method of adding the component (C-2) to thecomponent (C-1), a method of adding the component (C-1) to the component(C-2), and a method of adding them simultaneously can be employed.

In addition, organoaluminumoxy compounds such as methylalumoxane can beused as the component [C]. Preferred organoaluminumoxy compounds used inthe present invention can be produced, for example, by the methods shownbelow, and are usually obtained as solutions in a hydrocarbon solvent.

(1) A method of adding an organoaluminum compound such astrialkylaluminum to a suspension, in a hydrocarbon medium, of a compoundcontaining adsorbed water or a salt containing crystal water, forexample, magnesium chloride hydrate, copper sulfate hydrate, aluminumsulfate hydrate, nickel sulfate hydrate, cerous chloride hydrate, or thelike, thereby allowing the adsorbed water or crystal water to react withthe organoaluminum compound.

(2) A method of allowing water, ice or water vapor to directly act on anorganoaluminum compound such as a trialkylaluminum in a medium such asbenzene, toluene, ethyl ether or tetrahydrofuran.

(3) A method of reacting an organoaluminum compound such as atrialkylaluminum with an organotin oxide such as dimethyltin oxide ordibutyltin oxide in a medium such as decane, benzene or toluene.

Examples of the organoaluminum compounds used for the preparation of theorganoaluminumoxy compounds are trialkylaluminum compounds such astrimethylaluminum, triethylaluminum, tripropylaluminum,triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum,tri-sec-butylaluminum, tri-tert-butylaluminum, tripentylaluminum,trihexylaluminum, trioctylaluminum and tridecylaluminum;tricycloalkylaluminum compounds such as tricyclohexylaluminum andtricyclooctylaluminum; dialkylaluminum halides such as dimethylaluminumchloride, diethylaluminum chloride, diethylaluminum bromide anddiisobutylaluminum chloride; dialkylaluminum hydrides such asdiethylaluminum hydride and diisobutylaluminum hydride; dialkylaluminumalkoxides such as dimethylaluminum methoxide and diethylaluminumethoxide; dialkylaluminum aryloxides such as diethylaluminum phenoxide;etc.

Of these compounds, trialkylaluminums and tricycloalkylaluminums arepreferred, and trimethylaluminum is especially preferred.

The organoaluminumoxy compounds are used in such a form as containing asmall amount of the organoaluminum compound which is a startingmaterial.

Method of combination of the components [A], [B] and [C] is notparticularly limited, and, for example, a method of previouslycontacting the component [B] with the component [C], and then contactingthe component [A] therewith, a method of previously contacting thecomponent[A] with the component [C], and then contacting the component[B] therewith, and the like can be employed. When the components arecontacted with each other, the contacting of the components [B] and [C]is preferably carried out in a good solvent for the component [B]. Whenthe component [A] is contacted with the other components [B] and [C],the contacting is preferably carried out in a poor solvent for thecomponent [B].

The good solvents for the component [B] include, for example, aromaticcompounds such as benzene, toluene and xylene. The poor solvents for thecomponent [B] include, for example, straight chain or branched chainhydrocarbon compounds such as isobutane, pentane, isopentane, hexane,heptane, octane, decane, dodecane and kerosene.

The amounts and the ratio of the amounts of these components are alsonot particularly limited, but it is preferred to use the component [C]in an amount sufficient to result in the reaction of the component [B].

In the present invention, the component [B] is used in an amount ofpreferably 5×10⁻⁶ to 10⁻² mol, more preferably 10⁻⁵ to 10⁻³ mol based on1 g of the component [A].

When the components [A], [B] and [C] are contacted, unreacted component[B] is sometimes present in the reaction solvent depending onconditions, and the unreacted component [B] is removed by washing with asolvent in which the component [B] is soluble or by heating and/ortreating under reduced pressure, or by other methods.

The solid catalyst component comprising [A], [B] and [C] of the presentinvention may be used as such or after being subjected toprepolymerization.

In the prepolymerization, it is desired that the component [B] is usedin an amount of preferably 1×10⁻⁵ to 5×10⁻³ mol, more preferably 5×10⁻⁵to 10⁻³ mol based on 1 g of the component [A]. The prepolymerizationtemperature is usually preferably −20° C.-80° C., more preferably 0°C.-50° C., and the prepolymerization time is usually preferably about0.5-100 hours, more preferably about 1-50 hours though it may varydepending on the prepolymerization temperature.

The amount of polymer produced by the prepolymerization is preferablyabout 0.1-500 g, more preferably 0.3-300 g, especially preferably 1-100g based on 1 g of the solid component.

The olefin used for the prepolymerization is preferably selected fromthe olefins used in the polymerization mentioned hereinafter. Of theolefins, ethylene is especially preferred.

The solid catalyst component comprising [A], [B] and [C] of the presentinvention is preferably added to a polymerizer as a slurry in analiphatic hydrocarbon or alicyclic hydrocarbon mentioned hereinafter.

Next, the component [D] used in the present invention will be describedbelow.

The compound [component (i)] represented by the formula(Mt)_(α)(Mg)_(β)(R¹)_(a)(R²)_(b) [in the formula, Mt is a metal atombelonging to Group 1-3 of the Periodic Table, R¹ and R² are hydrocarbongroups of 2-20 carbon atoms, and α, β, a and b are numerals satisfyingthe following relations: 0≦α, 0<β, 0≦a, 0≦b, a+b>0, and rα+2β=a+b (wherer is a valence of Mt)] is shown herein in the form of a complex compoundof organomagnesium, nevertheless, it is meant to include all of the R₂Mgand complexes thereof with other metal compounds. The relationshiprα+2β=a+b among α, β, a and b shows the stoichiometry of the valence ofthe metal atom and the substituent.

The hydrocarbon groups represented by R¹ and R² are alkyl groups,cycloalkyl groups or aryl groups, and include, for example, a methylgroup, ethyl group, n-propyl group, isopropyl group, n-butyl group,isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexylgroup, octyl group, decyl group, phenyl group, tolyl group, etc. R¹ ispreferably an alkyl group, and especially preferably a primary alkylgroup.

In the case of α>0, as the metal atom Mt, the metal elements belongingto Groups 1-3 of the Periodic Table can be used, and examples thereofinclude lithium, sodium, potassium, beryllium, zinc, boron, aluminum,etc., and especially preferred are aluminum, boron, beryllium and zinc.

The ratio of magnesium to the metal atom Mt, namely, β/α can beoptionally set, but is preferably 0.1-50, especially preferably 0.5-10.Furthermore, when a certain organomagnesium compound of α=0 is used, inthe case of R¹ being, for example, sec-butyl, the compound is soluble ina hydrocarbon solvent and such compound also gives preferable results inthe present invention.

R¹ and R² in the case of α=0 in the formula(Mt)_(α)(Mg)_(β)(R¹)_(a)(R²)_(b) are desirably one of the followingthree groups (1), (2) and (3).

(1) At least one of R¹ and R² is a secondary or a tertiary alkyl groupof 4-6 carbon atoms, preferably both of R¹ and R² have 4-6 carbon atomsand at least one of them is a secondary or tertiary alkyl group.

(2) R¹ and R² are alkyl groups different in the number of carbon atoms,preferably R¹ is an alkyl group of 2 or 3 carbon atoms and R² is analkyl group of 4 or more carbon atoms.

(3) At least one of R¹ and R² is a hydrocarbon group of 6 or more carbonatoms, preferably R¹ and R² are both alkyl groups of 6 or more carbonatoms.

These groups will be specifically shown below.

Examples of the secondary or tertiary alkyl groups of 4-6 carbon atomsin the above (1) include sec-butyl, tert-butyl, 2-methylbutyl,2-ethylpropyl, 2,2-dimethylpropyl, 2-methylpentyl, 2-ethylbutyl,2,2-dimethylbutyl, 2-methyl-2-ethylpropyl, etc., and sec-butyl isespecially preferred.

Examples of the alkyl groups of 2 or 3 carbon atom in the above (2)include an ethyl group and propyl group, and an ethyl group isespecially preferred. Examples of the alkyl groups of 4 or more carbonatoms include a butyl group, amyl group, hexyl group, octyl group, etc.,and a butyl group and hexyl group are especially preferred.

Examples of the alkyl groups of 6 or more carbon atoms in the above (3)include a hexyl group, octyl group, decyl group, phenyl group, etc., andan alkyl group is preferred, and a hexyl group is especially preferred.

In general, when the number of carbon atoms of the alkyl groupincreases, the compound becomes more soluble in a hydrocarbon solvent,but the viscosity of the solution thereof tends to become higher, andthus the use of alkyl groups of unnecessarily long chain alkyl groups isnot preferred from the point of handling. The above organomagnesiumcompounds are used in the form of a solution in hydrocarbon, and even ifa slight amount of a complexing agent such as ether, ester or amine iscontained or remains in the solution, it can be used without anyproblem.

Next, the compound [component (ii)] to be reacted with theorganomagnesium compound (i) will be described. This compound isselected from amine, alcohol and siloxane compounds.

The amine compounds include, for example, aliphatic, alicyclic andaromatic amines, and examples thereof include methylamine,dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine,butylamine, dibutylamine, tributylamine, hexylamine, dihexylamine,trihexylamine, octylamine, dioctylamine, trioctylamine, aniline,N-methylaniline, N,N-dimethylaniline, toluidine, etc.

Examples of the alcohol compounds include ethyl alcohol, n-butylalcohol, sec-butyl alcohol, tert-butyl alcohol, amyl alcohol, hexylalcohol, 2-methylpentyl alcohol, 2-ethylbutyl alcohol, 2-ethylpentylalcohol, 2-ethylhexyl alcohol, 2-ethyl-4-methylpentyl alcohol,2-propylheptyl alcohol, 2-ethyl-5-methyloctyl alcohol, n-octyl alcohol,n-decyl alcohol, cyclohexanol, phenol, etc. Preferred are n-butylalcohol, sec-butyl alcohol, 2-methylpentyl alcohol and 2-ethylhexylalcohol.

The siloxane compounds will be described below. They include siloxanecompounds having constitutive units represented by the following generalformula (11):

The substituents R⁴ and R⁵ are hydrogen or groups selected from thegroup consisting of hydrocarbon groups of 1-30 carbon atoms andsubstituted hydrocarbon groups of 1-40 carbon atoms, and examples of thehydrocarbon groups include a methyl group, ethyl group, n-propyl group,isopropyl group, n-butyl group, isobutyl group, sec-butyl group,tert-butyl group, pentyl group, hexyl group, octyl group, decyl group,phenyl group, tolyl group, vinyl group, etc.

Examples of the substituted hydrocarbon groups include a trifluoropropylgroup, etc.

These compounds can be used in the form of chain or cyclic compounds ofdimers or higher polymers which comprise one or two or more differentconstitutive units.

Examples of the siloxane compounds include symmetricdihydrotetramethyldisiloxane, hexamethyldisiloxane,hexamethyltrisiloxane, pentamethyltrihydrotrisiloxane, cyclicmethylhydrotetrasiloxane, cyclic methylhydropentasiloxane, cyclicdimethyltetrasiloxane, cyclic methyltrifluoropropyltetrasiloxane, cyclicmethylphenyltetrasiloxane, cyclic diphenyltetrasiloxane, (terminaltrimethylsilyl-capped) methylhydropolysiloxane, dimethylpolysiloxane,(terminal trimethylsilyl-capped) phenylhydropolysiloxane,methylphenylpolysiloxane, etc.

The reaction between the component (ii) and the component (i) can becarried out at a temperature between room temperature and 150° C. in aninert reaction medium, for example, an aliphatic hydrocarbon such ashexane, heptane or the like or an aromatic hydrocarbon such as benzene,toluene or the like. As for the sequence of the reaction, any of amethod of adding the component (ii) to the component (i), a method ofadding the component (i) to the component (ii), and a method of addingthem simultaneously can be employed. The reaction ratio of the component(i) and the component (ii) is not particularly limited, but the range ofmolar ratio of the component (ii) to the total metal atoms in theorganomagnesium component resulting from the reaction is 0.01-2,preferably 0.1-1.

In the present invention, the component [D] may be used either alone orin combination.

In the present invention, the component [D] is used as a scavenger. Thiscomponent [D], even in a high concentration, hardly decreases thepolymerization activity of the catalyst, and thus a high polymerizationactivity of the catalyst can be maintained in a wide range of scavengerconcentration. Therefore, the polymerization activity of the catalystfor olefin polymerization containing the component [D] can be easilycontrolled.

The concentration of the component [D] in the use for polymerization is0.001-10 mmols/liter, preferably 0.01-5 mmols/liter in totalconcentration when the sum of the mol numbers of the organometalliccompounds is assumed to be the total mol number.

Next, a specific embodiment of carrying out the polymerization of olefinin the presence of the catalyst of the present invention will bedescribed below. Using the catalyst for polymerization of olefins of thepresent invention, ethylene can be homopolymerized or copolymerized withat least one olefin, preferably selected from the group consisting of anα-olefin of 3-20 carbon atoms, a cyclic olefin of 3-20 carbon atoms, acompound represented by the formula CH₂═CHR (where R is an aryl group of6-20 carbon atoms) and a straight chain, branched chain or cyclic dieneof 4-20 carbon atoms.

In the present invention, the α-olefin of 3-20 carbon atoms is selectedfrom the group consisting of, for example, propylene, 1-butene,1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; the cyclicolefin of 3-20 carbon atoms is selected from the group consisting of,for example, cyclopentene, cyclohexene, cycloheptene, norbornene,5-methyl-2-norbornene, tetracyclododecene and2-methyl-1.4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene; thecompound represented by the formula CH₂═CHR (where R is an aryl group of6-20 carbon atoms) is, for example, styrene, vinylcyclohexane, etc.; andthe straight chain, branched chain or cyclic diene of 4-20 carbon atomsis selected from the group consisting of, for example, 1,3-butadiene,1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene and cyclohexadiene.

By the copolymerization of ethylene and the above olefins (comonomers),the density or physical properties of the ethylene polymers can becontrolled. The polymerization of olefins in the present invention canbe performed by either a suspension polymerization method or gas phasepolymerization method. In the suspension polymerization method, an inerthydrocarbon medium can be used as a medium for the suspensionpolymerization, and the olefin per se can also be used as the solvent.

Examples of the inert hydrocarbon media include aliphatic hydrocarbonssuch as propane, butane, isobutane, pentane, isopentane, hexane,heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbonssuch as cyclopentane, cyclohexane and methylcyclopentane; aromatichydrocarbons such as benzene, toluene and xylene; halogenatedhydrocarbons such as ethyl chloride, chlorobenzene and dichloromethane;mixtures of these hydrocarbons; etc.

In the polymerization of ethylene using the catalyst for olefinpolymerization of the present invention it is preferred that the amountof the solid catalyst component fed to the polymerization system forhomopolymerizing or copolymerizing ethylene is controlled so that theamount of the solid catalyst component becomes, for example, 1 to 0.001%by weight based on the total weight of the polymer obtained per hour.The polymerization temperature is preferably not lower than 0° C., morepreferably not lower than 50° C., further preferably not lower than 60°C. and not higher than 150° C., preferably not higher than 110° C.,further preferably not higher than 100° C. Further, the polymerizationtemperature is, preferably 0° C.-150° C., more preferably 50° C.-110° C.and still more preferably 60° C.-100° C. The polymerization pressure ispreferably between atmospheric pressure and 10 MPa, more preferably0.2-5 MPa, further preferably 0.5-3 MPa. The polymerization reaction canbe carried out by any of a batch method, semi-continuous method andcontinuous method. Moreover, the polymerization can be carried out intwo or more stages differing in reaction conditions.

Furthermore, as disclosed, for example, in DE3127133.2, the molecularweight of the resulting olefin polymer can also be adjusted by allowinghydrogen to be present in the polymerization system or by changing thepolymerization temperature. The catalyst for olefin polymerization ofthe present invention can contain other components useful for olefinpolymerization in addition to the above-mentioned components.

The present invention will be further specifically described by way ofthe following examples and comparative examples.

EXAMPLE 1

(Preparation of the Component [A]):

One gram of Silica P-10 (manufactured by Fuji Silicia Co., Ltd. (Japan))was calcinated at 400° C. for 5 hours in a nitrogen atmosphere to bedehydrated. The amount of hydroxyl group on the surface of thedehydrated silica was 1.3 mmol/g-SiO₂. One gram of this dehydratedsilica was dispersed in 40 ml of hexane to obtain a slurry. To theresulting slurry was added 1.5 ml of a solution of triethylaluminum inhexane (concentration: 1 M), followed by stirring for 1 hour, wherebytriethylaluminum and hydroxyl groups on the surface of the silica werereacted to obtain the component [A] wherein all of the hydroxyl groupson the surface have been treated with triethylaluminum. Then, thesupernatant liquid in the resulting reaction mixture was removed bydecantation, thereby removing unreacted triethylaluminum in thesupernatant liquid. Thereafter, a suitable amount of hexane was added toobtain 50 ml of a hexane slurry of the triethylaluminum-treated silica.

(Preparation of Catalyst Supported on Silica):

1.14 Gram of bis(hydrogenated tallowalkyl)methylammonium-tris(pentafluorophenyl)(4-hydroxyphenyl) borate(hereinafter referred to as “borate”) was added to 10 ml of toluene anddissolved therein to obtain a 0.1M solution of the borate in toluene.

To this solution of borate in toluene was added 1 ml of a 1M solution ofdiethylethoxyaluminum in toluene at room temperature and further toluenewas added thereto so that the borate concentration in the toluenesolution reached 50 mM. Thereafter, the solution was stirred at roomtemperature for 1 hour to obtain a reaction mixture containing borate.

1.2 Milliliter of this reaction mixture containing borate was added to50 ml of the slurry of the component [A] obtained as above, followed bystirring for 1 hour to support the borate on the silica by physicaladsorption. Thus, a slurry of silica supporting the borate was obtained.

To the resulting slurry was added 0.6 ml of a solution obtained bydissolving 10 mmols of[(N-t-butylamide)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilane]titanium-1,3-pentadiene (hereinafter referred to as“titanium complex”) in 100 ml of Isopar E (trademark for a hydrocarbonmixture manufactured by Exxon Chemical Co., Ltd. (USA)), followed bystirring for 3 hours to react the titanium complex with the borate.Thus, a reaction mixture was obtained which contained silica and asupernatant liquid and in which a catalytically active species wasformed on the silica.

(Preparation of Component [D]):

In a flask of 200 ml were charged 40 ml of hexane and an organomagnesiumcompound represented by AlMg₆ (C₂H₅) 3 (n-C₄H₉)₁₂ in an amount of 37.8mmols in terms of Mg+Al, and 40 ml of hexane containing 2.27 g (37.8mmols) of methylhydropolysiloxane (viscosity at 25° C.: 20 centistokes)was added thereto at 25° C., followed by raising the temperature to 80°C. and carrying out the reaction for 3 hours with stirring to obtain thecomponent [D].

(Copolymerization of Ethylene with 1-hexene):

800 Milliliters of hexane was charged in an autoclave of 1.8 liters involume, and the above component [D] was added thereto in an amount of0.2 mmol in terms of Mg+Al. In this autoclave was charged pressurizedethylene to raise the internal pressure of the autoclave to 1 MPa, andfurthermore 15 ml of 1-hexene was charged in the autoclave. Then, theinternal temperature of the autoclave was raised to 75° C., and theslurry of catalyst supported on silica obtained as above was added insuch an amount that the weight of the catalyst was 20 mg to start thecopolymerization of ethylene and 1-hexene. The copolymerization wascarried out for 30 minutes while adding ethylene to the autoclave sothat the internal pressure of the autoclave was maintained at 1 MPa.After completion of the copolymerization, the reaction mixture (a slurryof the copolymer) was extracted from the autoclave, and the catalyst wasdeactivated with methanol. Thereafter, the reaction mixture wasfiltered, washed and dried to obtain 120 g of dry powder of thecopolymer. The inside of the autoclave was inspected to find nodeposition of the polymer on the inner wall, etc. of the autoclave. Thecatalytic activity was 2507 kg-PE/g-Ti.

The resulting powder of the copolymer had an average particle diameterof 340 μm and a bulk density of 0.35 g/cm³, and showed markedlyexcellent fluidity. Thus, it was recognized that the resulting powder ofthe copolymer had remarkably excellent particle properties.

COMPARATIVE EXAMPLE 1

(Copolymerization of Ethylene and 1-hexene):

Copolymerization was carried out in the same manner as in Example 1,except that 0.2 mmol of butylethylmagnesium was used in place of thecomponent [D]. After completion of the copolymerization, the reactionmixture (a slurry of the copolymer) was extracted from the autoclave,and the catalyst was deactivated with methanol. Thereafter, the reactionmixture was filtered, washed and dried to obtain 50 g of dry powder ofthe copolymer. The inside of the autoclave was inspected, and nodeposition of the polymer on the inner wall, etc. of the autoclave wasfound. The catalytic activity of the catalyst was 1044 kg-PE/g-Ti.

The resulting powder of the copolymer had an average particle diameterof 250 μm and a bulk density of 0.28 g/cm³.

COMPARATIVE EXAMPLE 2

(Copolymerization of Ethylene and 1-hexene):

Copolymerization was carried out in the same manner as in Example 1,except that 0.2 mmol of triethylaluminum was used in place of thecomponent [D]. After completion of the copolymerization, the reactionmixture (a slurry of the copolymer) was extracted from the autoclave,and the catalyst was deactivated with methanol. Thereafter, the reactionmixture was filtered, washed and dried to obtain 20 g of dry powder ofthe copolymer. The inside of the autoclave was inspected, and depositionof the polymer on the inner wall, etc. of the autoclave was found. Thecatalytic activity of the catalyst was 418 kg-PE/g-Ti.

The resulting powder of the copolymer had an average particle diameterof 200 μm and a bulk density of 0.21 g/cm³.

COMPARATIVE EXAMPLE 3

(Copolymerization of Ethylene and 1-hexene):

Copolymerization was carried out in the same manner as in Example 1,except that 0.2 mmol of triisobutylaluminum was used in place of thecomponent [D]. After completion of the copolymerization, the reactionmixture (a slurry of the copolymer) was extracted from the autoclave,and the catalyst was deactivated with methanol. Thereafter, the reactionmixture was filtered, washed and dried to obtain 95 g of a dry powder ofthe copolymer. The inside of the autoclave was inspected, and depositionof the polymer on the inner wall, etc. of the autoclave was found. Thecatalytic activity of the catalyst was 1984 kg-PE/g-Ti. The resultingpowder of the copolymer had an average particle diameter of 320 μm and abulk density of 0.26 g/cm³.

EXAMPLE 2

(Preparation of the Component [D]):

In a flask of 200 ml were charged 40 ml of hexane and an organomagnesiumcompound represented by AlMg₆(C₂H₅)₃(n-C₄H₉)₁₂ in an amount of 37.8mmols in terms of Mg+Al, and 40 ml of hexane containing 37.8 mmols ofn-butyl alcohol was added, followed by raising the temperature to 80° C.and carrying out the reaction for 3 hours with stirring to obtain thecomponent [D].

(Copolymerization of Ethylene and 1-hexene):

Copolymerization was carried out in the same manner as in Example 1,except that the component [D] was changed to the one obtained as above.After completion of the copolymerization, the reaction mixture (a slurryof the copolymer) was extracted from the autoclave, and the catalyst wasdeactivated with methanol. Thereafter, the reaction mixture wasfiltered, washed and dried to obtain 82 g of a dry powder of thecopolymer. The inside of the autoclave was inspected, and no depositionof the polymer on the inner wall, etc. of the autoclave was found. Thecatalytic activity of the catalyst was 1713 kg-PE/g-Ti.

The resulting powder of the copolymer had an average particle diameterof 300 μm and a bulk density of 0.34 g/cm³, and had a markedly excellentfluidity. Thus, it was recognized that the resulting powder of thecopolymer showed markedly excellent particle properties.

EXAMPLE 3

(Preparation of Methylalumoxane-Supporting Silica)

Four grams of silica (manufactured by Fuji Silicia Co., Ltd. (Japan);pore volume: 1.10 cm³/g, specific surface area: 318 m²/g, bulk density:0.38 g/cm³, amount of hydroxyl group: 4.1 wt %) and 40 ml of toluenewere charged into a glass flask of 300 ml, the inside of which wassufficiently replaced with nitrogen to make a slurry, and the slurry wascooled to −10° C. To this slurry was added dropwise 70 ml of a solutionof methylalumoxane (manufactured by Albermar Co. (USA)) in toluene (Alconcentration: 1 mol/l) over a period of 1 hour while keeping thetemperature of the system at −10° C. Thereafter, the reaction wascarried out at 0° C. for 1 hour, at room temperature for 1 hour, and at110° C. for 3 hours. Generation of methane gas occurred during a seriesof the operations. Thereafter, the reaction product was cooled to 20° C.to obtain a slurry of silica on which methylalumoxane was supported andin which all of the hydroxyl groups on the surface of the silica wereremoved.

(Preparation of Catalyst Supported on Silica):

To the resulting slurry was added a solution ofbis(n-butylcyclopentadienyl)zirconium dichloride in toluene (2.5mmols/liter) in an amount of 0.24 mmol in terms of zirconium, and thereaction was carried out at 50° C. for 3 hours. Thus, a reaction mixturecomprising silica on which catalytically active species was formed wasobtained.

(Copolymerization of Ethylene and 1-hexene):

800 Milliliters of hexane was charged into an autoclave of 1.8 liters involume, and the component [D] as used in Example 1 was added thereto inan amount of 0.2 mmol in terms of Mg⁺ Al. In this autoclave was chargedpressurized ethylene to raise the internal pressure of the autoclave to1 MPa, and furthermore 10 ml of 1-hexene was charged into the autoclave.Then, the internal temperature of the autoclave was raised to 75° C.,and the slurry of the solid catalyst as obtained above was added in suchan amount that the weight of the solid catalyst was 30 mg to start thecopolymerization of ethylene and 1-hexene. The copolymerization wascarried out for 30 minutes while adding ethylene to the autoclave sothat the internal pressure of the autoclave was maintained at 1 MPa.After completion of the copolymerization, the reaction mixture (a slurryof the copolymer) was extracted from the autoclave, and the catalyst wasdeactivated with methanol. Thereafter, the reaction mixture wasfiltered, washed and dried to obtain 180 g of dry powder of thecopolymer. The inside of the autoclave was inspected, and no depositionof the polymer on the inner wall, etc. of the autoclave was found. Thecatalytic activity of the catalyst was 1310 kg-PE/g-Zr.

The resulting powder of the copolymer had an average particle diameterof 470 μm and a bulk density of 0.32 g/cm³, and showed markedlyexcellent fluidity. Thus, it was recognized that the resulting powder ofthe copolymer had markedly excellent particle properties.

EXAMPLE 4

(Preparation of Catalyst Supported on Montmorillonite):

70 Grams of commercially available granulated montmorillonite (BENCLAYSL having an average particle diameter of 16.2 μm manufactured byMizusawa Chemical Co., Ltd.) was dispersed in 500 ml of ion-exchangedwater in which 100 g of magnesium sulfate heptahydrate and 80 g ofsulfuric acid were dissolved, and the dispersion was heated up to 100°C. in 2 hours and kept at that temperature for 2 hours. Then, it wascooled down to 50° C. in 1 hour. The resulting slurry was filtered underreduced pressure, and a recovered solid was dried at 110° C. overnightin a nitrogen atmosphere to obtain 60 g of chemically treatedmontmorillonite.

10 Grams of the above chemically treated montmorillonite was introduced,followed by adding toluene and a solution of triethylaluminum (5 mmols)in hexane and stirring at room temperature. After a lapse of 1 hour,washing with hexane was carried out to prepare 200 ml of a hexaneslurry.

Then, to the slurry was added 65 ml of a toluene slurry ofethylenebis(indenyl)hafniumdimethyl (0.2 mmol) at room temperature, andreaction was carried out for 1 hour with stirring to obtain a reactionmixture comprising montmorillonite on which a catalytically activespecies was formed.

(Copolymerization of Ethylene and 1-hexene):

Polymerization reaction was carried out in the same manner as in Example3, except that the polymerization time was 1 hour in place of 30minutes, to obtain 40 g of a copolymer. The inside of the autoclave wasinspected, and no deposition of the polymer on the inner wall, etc. ofthe autoclave was found. The catalytic activity of the catalyst was 600kg-PE/g-Hf.

The resulting powder of the copolymer had an average particle diameterof 210 μm and a bulk density of 0.32 g/cm³, and showed markedlyexcellent fluidity. Thus, it was recognized that the resulting powder ofthe copolymer had markedly excellent particle properties.

EXAMPLE 5

Preparation of catalyst and polymerization were carried out in the samemanner as in Example 1, except that 0.3 mmol ofN,N′-bis(2,6-diisopropylphenyl)-2,3-butanediiminenickel (II) chloridewas used in place of[(N-t-butylamide)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilane]titanium-1,3-pentadiene,to obtain 17 g of a copolymer. The inside of the autoclave wasinspected, and no deposition of the polymer on the inner wall, etc. ofthe autoclave was found. The catalytic activity of the catalyst was 122kg-PE/g-Ni.

The resulting powder of the copolymer had an average particle diameterof 190 μm and a bulk density of 0.33 g/cm³, and showed markedlyexcellent fluidity. Thus, it was recognized that the resulting powder ofthe copolymer had markedly excellent particle properties.

EXAMPLES 6-19

Preparation of catalyst and polymerization reaction were carried out inthe same manner as in Example 1, except that the components [D] as shownin Table 1 were used, to obtain the results as shown in Table 1. Nodeposition of the polymer on the inner wall, etc. of the autoclave wasfound in any of the polymerizations.

TABLE 1 Component [D] Molar ratio of component (ii) Results ofpolymerization to the molar Average amount of Mg + Activity particleBulk Exam- Al in component Yield kg-PE/ diameter density ple Component(i) Component (ii) (i) g g-Ti μm g/cm³ 6 AlMg₅₀(C₂H₅)₃(n-C₄H₉)₁₀₀Methylhydropolysiloxane 1 100 2089 330 0.34 7 AlMg₉(C₂H₅)₃(n-C₄H₉)₁₈Methylhydropolysiloxane 1 110 2297 340 0.35 8 Mg(C₆H₁₃)₂Methylhydropolysiloxane 1 100 2089 330 0.33 9 AlMg₆(C₂H₅)₃(n-C₄H₉)₁₂Methylhydropolysiloxane 0.5 95 1984 330 0.32 10 AlMg₆(C₂H₅)₃(n-C₄H₉)₁₂Methylhydropolysiloxane 2 110 2297 340 0.34 11 AlMg₆(C₂H₅)₃(n-C₄H₉)₁₂Dimethylpolysiloxane 1 90 1880 320 0.33 12 AlMg₆(C₂H₅)₃(n-C₄H₉)₁₂Octamethylcyclotetrasiloxane 1 100 2089 330 0.34 13AlMg₆(C₂H₅)₃(n-C₄H₉)₁₂ Phenylhydropolysiloxane 0.8 95 1984 330 0.33 14AlMg₄(C₂H₅)₃(n-C₆H₁₃)₄ Symmetrical tetramethyl- 1 110 2297 340 0.33dihydroxydisiloxane 15 Mg(n-C₄H₉)_(1.5)(n-C₈H₁₇)_(0.5) Cyclicmethylhydrotetrasiloxane 0.5 80 1671 310 0.31 16 Mg(sec-C₄H₉)₂ Cyclicethoxymethyl- 1 100 2089 330 0.33 pentasiloxane 17AlMg₆(C₂H₅)₃(n-C₄H₉)₁₂ 2-Ethylhexyl alcohol 1 70 1462 300 0.32 18AlMg₆(C₂H₅)₃(n-C₄H₉)₁₂ Dioctylamine 1 80 1671 310 0.34 19AlMg₆(C₂H₅)₃(n-C₄H₉)₁₂ Methylhydropolysiloxane + 0.5 + 0.5 85 1775 3200.32 n-butanol

INDUSTRIAL APPLICABILITY

The catalysts for olefin polymerization according to the presentinvention can be applied to suspension polymerization (slurrypolymerization) or gas phase polymerization of olefins. The presentinvention provides the catalysts for olefin polymerization comprisingthe scavenger that can maintain high polymerization activity of thecatalyst in a wide range of scavenger concentration as well as themethod for polymerizing olefins using the above catalyst, that producepolymer powder causing no phenomena such as deposition on the reactorand having markedly excellent particle properties.

1. A catalyst for olefin polymerization, comprising: a solid catalystcomponent comprising: [A] a solid component having no hydroxyl group,[B] a compound of a transition metal selected from Groups 3-11 of thePeriodic Table, and [C] a mixture of an activator compound (C-1) capableof reacting with the transition metal compound [B] to form a metalcomplex having catalytic activity and an organoaluminum compound (C-2);and [D] an organomagnesium compound soluble in a hydrocarbon solventwhich is obtained by reacting (i) an organomagnesium compoundrepresented by the general formula:(Mt)_(α)(Mg)_(β)(R¹)_(a)(R²)_(b) wherein Mt is a metal atom belonging toGroups 1-3 of the Periodic Table, R¹ and R² are hydrocarbon groups of2-20 carbon atoms, and α, β, a and b are numerals satisfying thefollowing relationship: 0≦α, 0<β, 0≦a, 0≦b, a+b>0, and rα+2β=a+b (wherer is a valence of Mt) with (ii) a compound selected from an aminecompound, an alcohol compound and a siloxane compound.
 2. A catalyst forolefin polymerization according to claim 1, wherein Mt is Al, B, Zn orBe.
 3. A catalyst for olefin polymerization according to claim 1 or 2,wherein α and β satisfy the relationship α>0 and 0.5≦β/α≦10.
 4. Acatalyst for olef in polymerization according to claim 1 or 2, whereinR¹ is a primary alkyl group.
 5. A catalyst for olef in polymerizationaccording to claim 1 or 2, wherein the compound [B] of a transitionmetal selected from Groups 3-11 of the Periodic Table is a compoundrepresented by the following formula (1):L_(j)W_(k)MX_(p)X′_(q)  (1) wherein L denotes independently a η-bondingcyclic anion ligand selected from the group consisting of acyclopentadienyl group, indenyl group, tetrahydroindenyl group,fluorenyl group, tetrahydrofluorenyl group and octahydrofluorenyl group,and the ligand may optionally have 1-8 substituents, and thesubstituents are those having 20 or less non-hydrogen atoms which areindependently selected from the group consisting of hydrocarbon groupsof 1-20 carbon atoms, halogen atoms, halogen-substituted hydrocarbongroups of 1-12 carbon atoms, aminohydrocarbyl groups of 1-12 carbonatoms, hydrocarbyloxy groups of 1-12 carbon atoms, dihydrocarbylaminogroups of 1-12 carbon atoms, hydrocarbyiphosphino groups of 1-12 carbonatoms, silyl groups, aminosilyl groups, hydrocarbyloxysily groups of1-12 carbon atoms, and halosilyl groups; M denotes a transition metalhaving a formal oxidation number of +2, +3 or +4 which is selected fromthe group consisting of the transition metals belonging to Group 4 ofthe Periodic Table and is η⁵-bonded to at least one ligand L; W is adivalent substituent having 50 or less non-hydrogen atoms and bondsmonovalently to L and M respectively, thereby to form a metallo-cycletogether with L and M; X denotes an anionic σ-bonding ligand having 60or less non-hydrogen atoms which is selected independently from thegroup consisting of monovalent anionic σ-bonding ligands, divalentanionic σ-bonding ligands bonding divalently to M and divalent anionicσ-bonding ligands bonding monovalently to L and M respectively; X′denotes independently a neutral Lewis base coordination compound having40 or less non-hydrogen atoms; j is 1 or 2, with a proviso that in thecase of j being 2, the two ligands L may optionally bond to each otherthrough a divalent group having 20 or less non-hydrogen atoms, and thedivalent group is selected from the group consisting of hydrocarbadiylgroups of 1-20 carbon atoms, halohydrocarbadjyl groups of 1-12 carbonatoms, hydrocarbyleneoxy groups of 1-12 carbon atoms,hydrocarbyleneamino groups of 1-12 carbon atoms, silanediyl groups,halosilanediyl groups, and silyleneamino groups; k is 0 or 1, and p is0, 1 or 2, with a proviso that in the case of X being a monovalentanionic σ-bonding ligand or a divalent anionic σ-bonding ligand bondingto L and M, p is an integer which is smaller by at least 1 than theformal oxidation number of M, and in the case of X being a divalentanionic σ-bonding ligand bonding only to M, p is an integer which issmaller by at least (j+1) than the formal oxidation number of N, and qis 0, 1 or
 2. 6. A catalyst for olefin polymerization according to claim1 or 2, wherein the activator compound (C-1) capable of reacting withthe transition metal compound [B] to form a metal complex havingcatalytic activity is a compound represented by the following formula(2):[L−H]^(d+)[M_(m)Q_(p)]^(d−)  (2) wherein [L-H]^(d+) denotes a protondonating Brφnsted acid, L denotes a neutral Lewis base, and d is aninteger of 1-7; [M_(m)Q_(p)]^(d−) denotes a compatible non-coordinationanion, M denotes a metal or metalloid belonging to Groups 5-15 of thePeriodic Table, Q is selected independently from the group consisting ofhydrides, halides, dihydrocarbylamide groups of 2-20 carbon atoms,hydrocarbyloxy groups of 1-30 carbon atoms, hydrocarbon groups of 1-30carbon atoms and substituted hydrocarbon groups of 1-40 carbon atoms,the number of Q, which is a halide, is 1 or less, m is an integer of1-7, p is an integer of 2-14, d is as defined above, and p−m =d).
 7. Amethod for production of polyolefins, comprising polymerizing orcopolymerizing olefins in the presence of the catalyst for olefinpolymerization according to claim 1 or 2.